JPS63264194A - Treatment of chemical cleaning waste solution - Google Patents
Treatment of chemical cleaning waste solutionInfo
- Publication number
- JPS63264194A JPS63264194A JP9852087A JP9852087A JPS63264194A JP S63264194 A JPS63264194 A JP S63264194A JP 9852087 A JP9852087 A JP 9852087A JP 9852087 A JP9852087 A JP 9852087A JP S63264194 A JPS63264194 A JP S63264194A
- Authority
- JP
- Japan
- Prior art keywords
- added
- soln
- acid
- cod
- waste liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002699 waste material Substances 0.000 title claims abstract description 40
- 239000000126 substance Substances 0.000 title claims abstract description 26
- 238000004140 cleaning Methods 0.000 title claims abstract description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 51
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 21
- 230000003647 oxidation Effects 0.000 claims abstract description 19
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 8
- 229960004275 glycolic acid Drugs 0.000 claims abstract description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002244 precipitate Substances 0.000 claims abstract description 7
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 6
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 230000003449 preventive effect Effects 0.000 claims abstract description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 4
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 42
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 238000006864 oxidative decomposition reaction Methods 0.000 claims description 9
- 150000007524 organic acids Chemical class 0.000 claims description 7
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 238000004062 sedimentation Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- -1 iron ion Chemical class 0.000 claims description 4
- 150000004692 metal hydroxides Chemical class 0.000 claims description 3
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001448 ferrous ion Inorganic materials 0.000 abstract description 6
- 150000004679 hydroxides Chemical class 0.000 abstract description 3
- 238000005554 pickling Methods 0.000 abstract 2
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 abstract 1
- 239000001354 calcium citrate Substances 0.000 abstract 1
- 235000013337 tricalcium citrate Nutrition 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 description 13
- 239000002253 acid Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 238000010979 pH adjustment Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 208000005156 Dehydration Diseases 0.000 description 3
- 239000012028 Fenton's reagent Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000010812 mixed waste Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- MGZTXXNFBIUONY-UHFFFAOYSA-N hydrogen peroxide;iron(2+);sulfuric acid Chemical compound [Fe+2].OO.OS(O)(=O)=O MGZTXXNFBIUONY-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- RFGNMWINQUUNKG-UHFFFAOYSA-N iron phosphoric acid Chemical compound [Fe].OP(O)(O)=O RFGNMWINQUUNKG-UHFFFAOYSA-N 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
Landscapes
- Removal Of Specific Substances (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は化学洗浄廃液の処理方法に関し、更に詳しくは
有機洗浄廃液及び防錆液を含む化学洗浄廃液を放流する
に際し、同廃液より有機物質（以下、ＣＯＤと略記する
）、重金属及び有害物質を除去する方法に関する。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for treating chemical cleaning waste liquid, and more specifically, when discharging chemical cleaning waste liquid containing organic cleaning waste liquid and rust preventive liquid, organic substances are removed from the waste liquid. (hereinafter abbreviated as COD), relates to a method for removing heavy metals and harmful substances.
火力プラント、化学ブラントのボイラ、熱交換器等の金
属表−に付着した酸化物スケール（主１ｃＦｅ３０４）
をくえん酸又はくえん酸とヒドロキシ酢酸とを混合した
有機酸に酸腐食抑制剤（以下インヒビターと略記する）
を添加した酸液で除去する酸洗浄及び酸洗後の金属表面
を防錆保護する防錆液処理を例えば火力プラントの貫流
ボイラに適用した場合の化学洗浄廃液の組成と性状の一
例を示せば第１表の如くである。Oxide scale (mainly 1cFe304) attached to metal surfaces of thermal power plants, chemical blunt boilers, heat exchangers, etc.
An acid corrosion inhibitor (hereinafter abbreviated as inhibitor) is added to citric acid or an organic acid mixture of citric acid and hydroxyacetic acid.
An example of the composition and properties of chemical cleaning waste liquid when acid cleaning is applied to a once-through boiler in a thermal power plant, for example, when acid cleaning is applied to a once-through boiler in a thermal power plant. As shown in Table 1.
第１表から判るように処理前の混合廃液には有害成分で
あるＣＯＤ、溶解鉄、ｐＨ（遊離酸）、及びりん酸塩な
どが多量含有されておシ、また廃液の色も暗褐色を呈し
ている。このような化学洗浄廃液は公害上そのｉま放流
することはできない。放流水質の基準値は第２表−例示
されるように地域自治体との公害防止協定などで決めら
れた規制値まで浄化処理することが必要である。As can be seen from Table 1, the mixed wastewater before treatment contains large amounts of harmful components such as COD, dissolved iron, pH (free acid), and phosphates, and the color of the wastewater is dark brown. It is showing. Such chemical cleaning waste liquid cannot be directly discharged due to pollution concerns. As shown in Table 2, the standard values for effluent water quality need to be purified to the regulatory values determined by pollution prevention agreements with local governments.
第２表 排水基準値
※ 固形浮遊物質
従来は、仁のような化学洗浄廃液の処理法として、焼却
処理、湿式による化学的処理又は化学的処理と電解処理
との併用処理等があるが、湿式による化学的処理におい
ては、ＣＯＤ除去法として酸性域において過酸化水素水
を添加して酸化処理し、次いで苛性アルカリ及び水酸化
力ｆｉ／Ｖウム等のアルカリを添加してｐＨを１０．６
〜１３程度まで上昇させて前記酸化処理において生成さ
れた酸化反応生成物を難溶性化合物とすると同時に廃液
中の金属イオンも難溶性の水酸化物として沈殿生成させ
た後、沈降分離する方法も知られている。Table 2 Effluent standard values* Solid suspended solids Conventionally, methods for treating chemical cleaning waste such as lint include incineration, wet chemical treatment, or a combination of chemical treatment and electrolytic treatment. In the chemical treatment using COD, hydrogen peroxide solution is added in an acidic region for oxidation treatment, and then alkali such as caustic alkali and hydroxide fi/Vum is added to lower the pH to 10.6.
There is also a known method in which the oxidation reaction product produced in the oxidation treatment is made into a poorly soluble compound by raising the oxidation reaction product to about 13%, and at the same time the metal ions in the waste liquid are precipitated as poorly soluble hydroxides, and then separated by sedimentation. It is being
上述した従来のような方法では、金属イオン及びシん酸
塩はほぼ完全に除去できるが、過酸化水素水による酸化
処理においてＣＯＤ成分であるくえん酸の酸化分解が完
全でな（、一部くえん−として残留があるため、ＣＯＤ
の除去に限界があり、第２表のＣＯＤ排水基準値を完全
に満足しないこと、又水酸化力μシウム及び苛性アルカ
リ等を添加して廃液中の金属イオンを水酸化物として完
全に沈殿生成きせる場合においてそのｐＨは１０．６〜
１３程度まで上昇させる必要があるため、沈降分嬌後の
上澄液及び°沈殿物の脱水時の処理液の放流に際しては
排水基準値ｐＨ５，８〜ａ６の範囲になるよう＃＋１整
する必要があるなどの欠点があった。In the conventional method described above, metal ions and sicrate can be almost completely removed, but the oxidative decomposition of citric acid, which is a COD component, is not complete in the oxidation treatment with hydrogen peroxide (some of the citric acid - Since there is residual COD
There is a limit to the removal of COD wastewater, and the COD wastewater standard value shown in Table 2 cannot be fully satisfied.Also, it is impossible to completely precipitate the metal ions in the wastewater as hydroxides by adding hydroxide power μsium, caustic alkali, etc. In case the pH is 10.6~
Since it is necessary to raise the pH to about 13, when discharging the supernatant liquid after sedimentation and the treated liquid during dehydration of sediment, it is necessary to adjust the pH to +1 so that the pH is within the range of the wastewater standard value 5.8 to A6. There were drawbacks such as:
本発明は上記従来法の欠点を解決すべく廃液中のＣＯＤ
を第２表の排水基準値内まで除去し、かつ排水基準値ｐ
Ｈ範囲内で無色透明の処理水を得る化学洗浄廃液の処理
方法を提供しようとするものである。The present invention aims to solve the above-mentioned drawbacks of the conventional method by reducing COD in waste liquid.
is removed to within the wastewater standard value in Table 2, and the wastewater standard value p
The present invention aims to provide a method for treating chemical cleaning waste liquid that obtains colorless and transparent treated water within the H range.
本発明はくえん酸又はくえん酸とヒドロキシ酢酸とを混
合した有機酸洗浄液及び防錆液を含む化学洗浄廃液の処
理において、同廃液に硫酸を添加してｐＨを１〜４．５
の範囲に調整したのち、第一鉄イオン（Ｆｅ”）ＩＪ１
度として２，０００’ｐ’ｐｍ以上になるよう硫酸第一
鉄を添加し、次に粉末の活性炭を添加し、さらに過酸化
水素水を廃液中のＣ０ＤＶＣ対し、１当量以上好ましく
は１．２当量添加して酸化分解し、次いで同ｙＡ液に水
酸化力ｐシウムを添加してｐＨを７〜ａ乙の範囲に調整
して廃液中の重金属（主に鉄イオン）、前記酸化処理に
おいて生成した蓚酸を重金属水酸化物、蓚酸力ｐシラふ
として沈殿生成させた後、沈殿物を沈降分離しその上澄
液はなんらｐ！（調整することなく、そのまま放流し、
沈殿物はブレスフィルター又は遠心分離機等の脱水処理
装置により脱水処理するようにした化学洗浄廃液の処理
方法である。In the treatment of chemical cleaning waste liquid containing citric acid or an organic acid cleaning liquid containing citric acid and hydroxyacetic acid mixed together and a rust preventive liquid, sulfuric acid is added to the waste liquid to adjust the pH to 1 to 4.5.
After adjusting to the range of ferrous ion (Fe”) IJ1
Ferrous sulfate is added so that the concentration is 2,000'p'pm or more, then powdered activated carbon is added, and hydrogen peroxide is added in an amount of 1 equivalent or more, preferably 1.2 equivalents, based on the CODVC in the waste liquid. Add an equivalent amount to oxidize and decompose, and then add psium hydroxide to the same solution to adjust the pH to a range of 7 to 1 to remove heavy metals (mainly iron ions) in the waste solution, which are generated during the oxidation treatment. After the oxalic acid is precipitated as a heavy metal hydroxide, oxalic acid is precipitated, the precipitate is separated by sedimentation, and the supernatant liquid is free of any p! (Release as is without adjustment,
Sedimentation is a method for treating chemical cleaning waste liquid that is dehydrated using a dehydration treatment device such as a breath filter or a centrifugal separator.
次に本発明の方法をさらに具体的に説明するため第１表
に示した組成及び性状の化学洗浄廃液を対象として述べ
る。Next, in order to explain the method of the present invention in more detail, chemical cleaning waste liquid having the composition and properties shown in Table 1 will be described.
まず廃液処理槽に酸洗浄廃ｅ１容、酸洗浄後の水洗水廃
液２容、最後に防錆廃液１容を受は入れた混合廃液に一
酸を添加してｐＨを１〜４．５の範囲に調整したのち、
第一鉄イオンＣＦｅ”）９度として２．０００ ｐｐｍ
以上ニナルよう硫酸第一鉄を追加添加し、次に粉末の
活性炭を添加し、さらに過酸化水素水を廃液中のＣ０Ｄ
Ｋ対し、１当量以上好ましくは１．２当量添加してＣＯ
Ｄ負荷成分である有機酸（くえん酸、ヒドロキシ酢酸）
、インヒビター及びヒドラジンを酸化分解し、次いで同
廃液に水酸化力μシウムを添加してｐＨを７〜ａ６の範
囲に調整する。このように一連の薬品添加に当ってはエ
アレーション等で廃液を強制的に攪拌するのが液の均−
化及び酸化反応速度を速める上で好ましい。First, 1 volume of acid washing waste e, 2 volumes of washing water waste after acid washing, and finally 1 volume of rust prevention waste were put into the waste liquid treatment tank. Monoacid was added to the mixed waste to adjust the pH to 1 to 4.5. After adjusting to the range,
Ferrous ion CFe”) 2.000 ppm as 9 degrees
Additional ferrous sulfate was added as described above, powdered activated carbon was added, and hydrogen peroxide was added to the COD in the waste liquid.
1 equivalent or more preferably 1.2 equivalents of CO are added to K.
Organic acids (citric acid, hydroxyacetic acid) that are D-loading components
, the inhibitor and hydrazine are oxidized and decomposed, and then μsium hydroxide is added to the waste solution to adjust the pH to a range of 7 to a6. In this way, when adding a series of chemicals, it is important to forcibly stir the waste liquid using aeration, etc. to keep the liquid even.
This is preferable in terms of accelerating the reaction rate of oxidation and oxidation.
次いで沈殿生成する重金属水酸化物（燐酸力〃シウム）
及び蓚酸力／Ｌ／Ｖウムはセットリングを行なって上澄
液と沈殿・物（以下スフツジという）に完全分離し、上
澄液とヌラツジの脱水処理液は何んらｐＨ調整すること
なく、そのまま放流し、スフツジは適宜な脱水処理装置
により脱水して焼却、その他の方法で処理する。Heavy metal hydroxide (phosphoric acid) is then precipitated.
The oxalic acid force/L/Vum is completely separated into supernatant liquid and precipitate/material (hereinafter referred to as sufutsuji) by settling, and the supernatant liquid and the dehydrated liquid of nuratsuji are completely separated without any pH adjustment. The waste is discharged as is, and the sulfate is dehydrated using an appropriate dehydration treatment device, then incinerated, or treated by other methods.
なお、上記廃液処理において過酸化水素の添加はＫｄ液
を攪拌しながら均一にゆつくシと時間をかけるのが好ま
しく、２〜３時間で注入するのが適当である。また添加
後の放置時間は１５時間以上が好ましい。ＣＯＤ負荷成
分である有機酸（（えん酸、ヒドロキシ酢酸）インヒビ
ター及びＵドフジンが過酸化水素水によって酸化分解し
、ＣＯＤを除去する機構はインヒビターについては化学
成分が明らかではないので判らないが、くえん酸、ヒド
ロキシ酢酸及びヒドラジンは下記の第１式乃至第３式に
示す化学反応によるためと考えられる。In addition, in the above-mentioned waste liquid treatment, it is preferable to add hydrogen peroxide over a period of time so that the Kd solution is uniformly and slowly added while stirring the Kd solution, and it is appropriate to add hydrogen peroxide over a period of 2 to 3 hours. Further, the standing time after addition is preferably 15 hours or more. The mechanism by which organic acid ((citric acid, hydroxyacetic acid) inhibitors and U-dofuzine, which are COD-loading components, are oxidized and decomposed by hydrogen peroxide and remove COD is not known because the chemical components of the inhibitors are not clear, but it is unclear. It is thought that this is because the acid, hydroxyacetic acid, and hydrazine undergo chemical reactions shown in the following formulas 1 to 3.
・・・第１式
過酸化水素は単独では酸化力は弱いが、酸性域で、第一
鉄イオンとの混合溶液はフェントン試薬としてすぐれた
酸化効果のあることが知られており、第１式乃至ｔ４３
式の過酸化水素による酸化分解反応はＦｅ”＋が触媒と
して強く働いていると考えられる。...Formula 1 Hydrogen peroxide alone has weak oxidizing power, but in the acidic range, a mixed solution with ferrous ions is known to have an excellent oxidizing effect as Fenton's reagent. ~t43
It is thought that Fe''+ acts strongly as a catalyst in the oxidative decomposition reaction by hydrogen peroxide in the formula.
ところが第１式のくえん酸の酸化分解においてはその酸
化率が完全でなく一部くえん酸として残留しており、Ｃ
ＯＤ除去に限界のあることを実験により確めた。すなわ
ち第１式の酸化率がは＃！？ １００ ％であれば第１
式で生成する蓚酸（ＣｚＨｚＯ＊）は後で添加する水酸
化力μシラ五等によって蓚酸カルシウム（ＣａＣ２Ｏ４
） としてほぼ１００−チ沈殿生成するため、その上
澄液のＣＯＤは数ｐｐｎ＋まで低下するはずであるが＠
１式の酸化率が完全でないためにＣＯＤとして４０〜６
０ ｐｐｍ程度残留する。However, in the oxidative decomposition of citric acid in formula 1, the oxidation rate is not complete and some remains as citric acid, resulting in C
It was confirmed through experiments that there is a limit to OD removal. In other words, the oxidation rate of the first equation is #! ? If it is 100%, it is the first
Oxalic acid (CzHzO*) produced by the formula is converted to calcium oxalate (CaC2O4
), the COD of the supernatant liquid should be reduced to several ppn+, since almost 100-ti precipitate is formed.
Because the oxidation rate of formula 1 is not complete, the COD is 40 to 6.
Approximately 0 ppm remains.
そこで本発明では過酸化水素水によるＣＯＤ酸化処理に
かいて予め粉末活性炭を併用添加しておくことにより、
くえん酸の酸化分解率がほぼ１００チまで達し、ＣＯＤ
成分を効果的に除去することを見いだした。Therefore, in the present invention, by adding powdered activated carbon in advance to the COD oxidation treatment using hydrogen peroxide solution,
The oxidative decomposition rate of citric acid reaches almost 100%, resulting in COD
It has been found that the components can be effectively removed.
即ち粉末の活性炭を併用添加することＫよシ第１式の酸
化分解がほぼ１０Ｇ−まで達するのはフェントン試薬に
対し活性炭が酸化分解触媒として強く働く作用があって
化学平衡はくえん酸が完全に酸化分解されるまで反応は
右方向に進むためと考えられる。ＣＯＤ酸化処理時にお
ける適正ｐＨ範囲は１〜４．５が好ましく、ｐＨ１未満
ではＣＯＤ除去率は悪くなる。又ｐ Ｈ４，５を越える
と過酸化水素と第一鉄イオン（Ｆｅ”）との相乗効果が
低下し、フェントン試薬としての酸化効率が悪くなる。In other words, by adding powdered activated carbon together, the oxidative decomposition of equation 1 reaches approximately 10 G- because activated carbon acts strongly as an oxidative decomposition catalyst for Fenton's reagent, and the chemical equilibrium is completely maintained by citric acid. This is thought to be because the reaction proceeds in the right direction until it is oxidized and decomposed. The appropriate pH range during COD oxidation treatment is preferably 1 to 4.5, and if the pH is less than 1, the COD removal rate will be poor. Moreover, when the pH exceeds 4.5, the synergistic effect between hydrogen peroxide and ferrous ions (Fe'') decreases, and the oxidation efficiency as a Fenton reagent deteriorates.
又ＣＯＤ酸化処理時における第一鉄イオン（Ｆｅ”）の
適正濃度は２、 Ｑ Ｑ Ｑ ｐｐｒｎ以上好ましくは
５．０００ ｐｐｍ程度が最適である。２． ＯＱ Ｑ
ｐｐｍ未満でもＣＯＤの酸化分解は進むが、ＣＯＤが
第２表の排水基準値までは低下しない。なお、へＯＯＯ
ｐｐｍを越えてもその効果は余シ変化ない。粉末活性炭
の添加濃度はα１〜０．５チが好ましい。実用に当たっ
ての過酸化水素、の添加量は、廃液のＣＯＤを測定する
ことにより決めればよいが、第２表の排水基準値内に処
理するためには、Ｃ０ＤＫ対し当量以上好ましくは１．
２当量の添加が必要である。本発明の処理方法によれば
化学洗浄廃液中のＣＯＤ、重金属（主に鉄イオン）、Ｓ
Ｓなどの有害物質を第２表の排水基準値内まで除去可能
となり、また赤潮発生の一要因物質といわれる燐酸塩の
除去もほぼ完全にでき、かつスフツジを沈降分離した上
澄液も無臭で無色透明にすることができるので、処理水
の放流に際しては何らｐＨ調整することなく、そのまま
放流できる。In addition, the appropriate concentration of ferrous ions (Fe'') during COD oxidation treatment is optimally at least 2.000 ppm, preferably about 5.000 ppm.
Even if it is less than ppm, oxidative decomposition of COD will proceed, but the COD will not fall to the wastewater standard value shown in Table 2. In addition, to OOO
Even if the amount exceeds ppm, the effect remains unchanged. The concentration of powdered activated carbon added is preferably α1 to 0.5. In practical use, the amount of hydrogen peroxide to be added may be determined by measuring the COD of the waste fluid, but in order to treat the waste water within the wastewater standard values shown in Table 2, it should be added in an amount equivalent to or more than CODK, preferably 1.
Addition of 2 equivalents is required. According to the treatment method of the present invention, COD, heavy metals (mainly iron ions), and S
It is possible to remove harmful substances such as S to within the wastewater standard values shown in Table 2, and it is also possible to almost completely remove phosphates, which are said to be a factor in the occurrence of red tide, and the supernatant liquid obtained by sedimentation and separation of the sufutsuji is also odorless. Since it can be made colorless and transparent, the treated water can be discharged as it is without any pH adjustment.
第３表に本発明の実施例を示す。 Table 3 shows examples of the present invention.
有機酸洗浄液及び防錆液を含む化学洗浄廃液の処理にお
いて下記のような試験を行なった。The following tests were conducted in the treatment of chemical cleaning waste liquids containing organic acid cleaning liquids and rust preventive liquids.
この試験は第１表に示した組成及び性状の化学洗浄廃液
を対象として行なったもので、（Ｄ−１）、（Ｄ−２）
、（Ｄ−４）の３種の混合廃液のそれぞれ１ｔに硫酸の
添加量をかえてｐＨを１〜４．５に調整したのち、第一
鉄イオン（Ｆｅ２＋）８度として２．０００−１０００
ｐｐｍになるよう硫酸第一鉄を添加し、次に’５）末
の活性炭をＣＬ２５％添加し攪拌しながらさらに過酸化
水素水を廃液中のＣＯＤ分に対し１〜１．５当量になる
よう約１時間かけて添加し、２時間攪拌を続けたのち、
約１５時間放置し、次いで攪拌しながら同廃液に水酸化
カルシウムを添加してｐＨを７〜ａ６に調整して水酸化
第二鉄（燐酸カルシウム）及び蓚酸力〜シウムを完全に
沈殿生成させ、その処理水のＣＯＤ、溶解鉄（燐酸）及
びＳＳ（固形浮遊物）を測定し、第３表の試験番号（２
）〜（７）、（９）〜（至）、（ロ）〜Ｃ１！３）の如
き結果を得た。また比較のため過酸化水素水による酸化
処理時において活性炭を添加しない場合の従来法につい
ても行なった（試験番号＠〜Ｃ１！？））。This test was conducted on chemical cleaning waste liquids with the composition and properties shown in Table 1. (D-1), (D-2)
After adjusting the pH to 1 to 4.5 by changing the amount of sulfuric acid added to 1 t of each of the three types of mixed waste liquid of (D-4),
Add ferrous sulfate so that the amount is ppm, then add 25% CL of activated carbon from '5), and add hydrogen peroxide solution while stirring so that the amount becomes 1 to 1.5 equivalents to the COD content in the waste liquid. After adding for about 1 hour and continuing stirring for 2 hours,
Leave to stand for about 15 hours, then add calcium hydroxide to the waste solution while stirring to adjust the pH to 7 to A6 to completely precipitate ferric hydroxide (calcium phosphate) and oxalic acid. The COD, dissolved iron (phosphoric acid) and SS (solid suspended solids) of the treated water were measured, and the test number (2) in Table 3 was measured.
)~(7), (9)~(to), (b)~C1!3) were obtained. For comparison, a conventional method in which activated carbon was not added during the oxidation treatment with hydrogen peroxide solution was also conducted (Test No. C1!?).
試験番号（１）、（８）、（転）の参考例は第１表に示
す混合廃液（Ｄ−１）、（Ｄ−２）、及び（Ｄ−４）で
廃液処理前の性状を示す。Reference examples of test numbers (1), (8), and (transfer) are mixed waste liquids (D-1), (D-2), and (D-4) shown in Table 1, and the properties before waste liquid treatment are shown. .
本発明方法により次のような効果が奏せられる。 The method of the present invention provides the following effects.
（１）過酸化水素水によるＣＯＤ酸化処理時において、
予め粉末活性炭を添加しておくことにより有機酸の酸化
分解反応が顕著に促進されＣ’ＯＤ成分を効果的に除去
し得た。(1) During COD oxidation treatment with hydrogen peroxide solution,
By adding powdered activated carbon in advance, the oxidative decomposition reaction of the organic acid was significantly promoted and the C'OD component could be effectively removed.
（２）上記（１）の作用効果によりＣＯＤ酸化処埠時の
適正ｐＨ範囲が１〜４．５と広くなったので処理が容易
になった。(2) Due to the effect of (1) above, the appropriate pH range during COD oxidation treatment has been widened to 1 to 4.5, making treatment easier.
（３） 酸化処理後のｐＨ調整は排水基準値ｐＨ範囲
内で無色透明の処理水が得られるので放流に際しては何
らｐＨ調整することなくそのまま放流可能となった。(3) Since the pH adjustment after oxidation treatment is within the pH range of wastewater standard value and clear and colorless treated water is obtained, it is now possible to discharge the water as it is without any pH adjustment.
Claims (1)
機酸洗浄液及び防錆液を含む化学洗浄液の処理において
、同廃液に硫酸を添加してｐＨを１〜４．５の範囲に調
整したのち、第一鉄イオン濃度として２，０００ｐｐｍ
以上になるよう硫酸第一鉄を添加し、次に粉末の活性炭
を添加し、さらに過酸化水素水を廃液中のＣＯＤに対し
１当量以上添加して酸化分解し、次いで同廃液に水酸化
カルシウムを添加してｐＨを７〜８．６の範囲に調整し
て廃液中の重金属、（主に鉄イオン）前記酸化処理にお
いて生成した蓚酸を重金属水酸化物、蓚酸カルシウムと
して沈殿、生成させた後、沈殿物を沈降分離することを
特徴とする化学洗浄廃液の処理方法。In the treatment of organic acid cleaning solutions containing citric acid or a mixture of citric acid and hydroxyacetic acid, and chemical cleaning solutions including rust preventive solutions, sulfuric acid is added to the waste solution to adjust the pH to a range of 1 to 4.5, and then 2,000 ppm as iron ion concentration
Ferrous sulfate was added to the above amount, then powdered activated carbon was added, hydrogen peroxide was added in an amount of 1 equivalent or more to the COD in the waste liquid for oxidative decomposition, and then calcium hydroxide was added to the waste liquid. is added to adjust the pH to a range of 7 to 8.6 to precipitate and produce heavy metals in the waste liquid (mainly iron ions) and oxalic acid produced in the oxidation treatment as heavy metal hydroxides and calcium oxalate. , a method for treating chemical cleaning waste liquid characterized by sedimentation and separation of precipitates.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62098520A JPH0714515B2 (en) | 1987-04-23 | 1987-04-23 | Chemical cleaning waste liquid treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62098520A JPH0714515B2 (en) | 1987-04-23 | 1987-04-23 | Chemical cleaning waste liquid treatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63264194A true JPS63264194A (en) | 1988-11-01 |
| JPH0714515B2 JPH0714515B2 (en) | 1995-02-22 |
Family
ID=14221932
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62098520A Expired - Lifetime JPH0714515B2 (en) | 1987-04-23 | 1987-04-23 | Chemical cleaning waste liquid treatment method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0714515B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11352289A (en) * | 1998-06-09 | 1999-12-24 | Daiki Engineering Co Ltd | Processing method for chemical decontamination waste liquid |
| JP2003202396A (en) * | 2002-01-08 | 2003-07-18 | Kyushu Electric Power Co Inc | Method for treating chemical decontamination waste liquid |
| CN104445756A (en) * | 2014-12-05 | 2015-03-25 | 绍兴奇彩化工有限公司 | Comprehensive treatment method for organic acid-containing wastewater and iron mud |
| JP2018086614A (en) * | 2016-11-28 | 2018-06-07 | 三菱瓦斯化学株式会社 | Method for treating oxidizing substance-containing waste water |
| CN114149048A (en) * | 2021-11-10 | 2022-03-08 | 武汉欧瑞景环保科技有限公司 | Composite water treatment agent and preparation method and use method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5135672A (en) * | 1974-09-20 | 1976-03-26 | Ebara Infilco | SANKASHORIHOHO |
| JPS5648290A (en) * | 1979-09-28 | 1981-05-01 | Taki Chem Co Ltd | Treatment of waste water containing organic substance |
| JPS58193787A (en) * | 1982-04-30 | 1983-11-11 | Kurita Kasen Kk | Treatment of chemical washing waste water |
| JPS59196796A (en) * | 1983-04-19 | 1984-11-08 | Mitsubishi Heavy Ind Ltd | Treatment of liquid waste |
-
1987
- 1987-04-23 JP JP62098520A patent/JPH0714515B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5135672A (en) * | 1974-09-20 | 1976-03-26 | Ebara Infilco | SANKASHORIHOHO |
| JPS5648290A (en) * | 1979-09-28 | 1981-05-01 | Taki Chem Co Ltd | Treatment of waste water containing organic substance |
| JPS58193787A (en) * | 1982-04-30 | 1983-11-11 | Kurita Kasen Kk | Treatment of chemical washing waste water |
| JPS59196796A (en) * | 1983-04-19 | 1984-11-08 | Mitsubishi Heavy Ind Ltd | Treatment of liquid waste |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11352289A (en) * | 1998-06-09 | 1999-12-24 | Daiki Engineering Co Ltd | Processing method for chemical decontamination waste liquid |
| JP2003202396A (en) * | 2002-01-08 | 2003-07-18 | Kyushu Electric Power Co Inc | Method for treating chemical decontamination waste liquid |
| CN104445756A (en) * | 2014-12-05 | 2015-03-25 | 绍兴奇彩化工有限公司 | Comprehensive treatment method for organic acid-containing wastewater and iron mud |
| CN104445756B (en) * | 2014-12-05 | 2016-09-14 | 浙江奇彩环境科技股份有限公司 | A kind of organic acid-bearing wastewater and the integrated conduct method of iron cement |
| JP2018086614A (en) * | 2016-11-28 | 2018-06-07 | 三菱瓦斯化学株式会社 | Method for treating oxidizing substance-containing waste water |
| CN114149048A (en) * | 2021-11-10 | 2022-03-08 | 武汉欧瑞景环保科技有限公司 | Composite water treatment agent and preparation method and use method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0714515B2 (en) | 1995-02-22 |
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